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CN-121972303-A - Nano lignin-based floatation desulfurization collector and preparation method and application thereof

CN121972303ACN 121972303 ACN121972303 ACN 121972303ACN-121972303-A

Abstract

The application relates to a nano lignin-based flotation desulfurization collector, and a preparation method and application thereof, and belongs to the technical field of mineral flotation. The collector comprises a nanoscale lignin core, and an alkyl chain and a sulfhydryl type collecting functional group grafted on the surface of the core. The mercapto-type collecting functional group realizes selective recognition and collecting by utilizing the specific chemical affinity of sulfur atoms and iron ions on the surface of pyrite. The nano-sized lignin core has particle morphology and high specific surface area, and after the collector is adsorbed on the surface of pyrite through mercapto functional groups, the core can be firmly anchored on minerals, so that the binding force between the collector and the minerals is enhanced. At the same time, the grafted alkyl chains impart hydrophobicity to the pyrite surface, promoting pyrite attachment to bubbles and flotation. In addition, the nanoscale lignan core has no affinity to diasporite, and can inhibit aluminum minerals from floating upwards. Through the synergistic effect, the collector realizes the efficient separation of pyrite and diasporite.

Inventors

  • GUO XIN
  • Du wuxing
  • XU KE
  • ZHANG MENG
  • ZHANG JIANQIANG
  • ZHANG ZHANYUN
  • MA JUNWEI
  • LIU ZHONGYUAN
  • WEI ZHAOBIN
  • ZHANG NAN
  • LI SHASHA
  • YAO JIE

Assignees

  • 中铝郑州有色金属研究院有限公司

Dates

Publication Date
20260505
Application Date
20260403

Claims (10)

  1. 1. A nano lignin-based flotation desulfurization collector, which is characterized by comprising a nano-sized lignin core, and an alkyl chain and a sulfhydryl collection functional group grafted on the surface of the core.
  2. 2. The collector of claim 1 wherein the thiol-based collection functional group is derived from at least one of butyl xanthate, isobutyl xanthate, amyl xanthate, isoamyl xanthate, ethionamide.
  3. 3. The collector of claim 1 or 2, wherein the nanoscale lignin core has an average hydrated particle size of 100nm to 300nm and a polydispersity PDI of 0.2 or less.
  4. 4. A method for preparing the nano lignin-based flotation desulfurization collector of any one of claims 1 to 3, which is characterized by comprising the steps of carrying out graft copolymerization reaction on nano lignin dispersion liquid, quaternary ammonium salt type surfactant and sulfhydryl collector in the presence of inert atmosphere and free radical initiator; The mass ratio of the nano-sized lignin solid in the nano-sized lignin dispersion liquid to the sulfhydryl collector is 1 (5-10), the mass of the free radical initiator is 10% -30% of the mass of the sulfhydryl collector, the grafting copolymerization reaction temperature is 50-90 ℃, and the grafting copolymerization reaction time is 20-30 hours.
  5. 5. The method according to claim 4, wherein the quaternary ammonium salt type surfactant is at least one of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, and/or, The free radical initiator is one of ammonium persulfate, potassium persulfate and azo diisobutylamidine hydrochloride.
  6. 6. The method of claim 4, wherein the method of preparing the nanoscale lignin dispersion comprises: Dissolving the pretreated lignin in an organic solvent, and stirring and dissolving to obtain a lignin organic solution; adding deionized water into the lignin organic solution, and performing dilution-induced self-assembly treatment to precipitate lignin to form nano particles, so as to obtain nano lignin suspension; Transferring the nano lignin suspension into a pretreated dialysis bag, and performing dialysis and purification treatment to remove organic solvent and small molecular impurities in the nano lignin suspension, thereby obtaining nano lignin dispersion; the pretreatment of the dialysis bag comprises the steps of putting a dialysis tube into deionized water containing sodium bicarbonate and EDTA disodium salt for boiling, putting the dialysis tube into the deionized water containing EDTA disodium salt for boiling again after washing, and soaking the dialysis tube into ethanol water solution for standby.
  7. 7. The method according to claim 6, wherein the organic solvent is at least one of methanol, absolute ethanol, isopropanol, acetone, tetrahydrofuran, N-dimethylformamide, and/or, The pretreatment lignin is one of alkali lignin, lignosulfonate, enzymolysis lignin and organic solvent lignin, and/or, In the lignin organic solution, the mass concentration of lignin is 1 mg/mL-50 mg/mL.
  8. 8. The method of claim 6, wherein in the dilution-induced self-assembly process, the volume ratio of deionized water to the lignin organic solution is (3-50): 1, and/or, In the dialysis purification treatment, deionized water is replaced every 8-12 hours, the molecular weight cut-off of a dialysis bag is not less than 3500 Da, and the dialysis time is more than 48 hours.
  9. 9. Use of the nano lignin-based flotation desulfurization collector according to any one of claims 1 to 3 in mineral flotation, characterized in that the nano lignin-based flotation desulfurization collector is used for selective flotation removal of pyrite in bauxite reverse flotation desulfurization operation.
  10. 10. The use according to claim 9, wherein the total amount of the collector used in the selective pyrite removal process is 400g/t raw ore to 700 g/t raw ore, and the pH of the flotation pulp is 4.0 to 9.0.

Description

Nano lignin-based floatation desulfurization collector and preparation method and application thereof Technical Field The application relates to the technical field of mineral flotation, in particular to a nano lignin-based flotation desulfurization collector and a preparation method and application thereof. Background In the field of mineral processing, flotation collectors are key agents that determine the efficiency of separation. Traditional collectors and synthetic small molecule collectors (such as xanthates) have certain collecting capacity on sulphide minerals, but have the problems of high cost, unfriendly environment and the like. The development of novel green collectors using renewable biomass resources has become a research hotspot. Lignin is considered to be a potential flotation agent-modifying feedstock because of its wide source, low cost, and the variety of reactive functional groups. However, when the common lignin is directly used for preparing the collector by modification, the collection efficiency and selectivity of the obtained product on target minerals are difficult to meet the industrial requirements, and the application of the lignin in the field of flotation medicaments is limited. Disclosure of Invention The application provides a nano lignin-based flotation desulfurization collector and a preparation method and application thereof, and aims to solve the technical problem of how to develop a high-efficiency and green flotation desulfurization collector with nano material characteristics and strong collection selectivity. In a first aspect, embodiments of the present application provide a nano lignin-based flotation desulfurization collector comprising a nano lignin core, and alkyl chains and mercapto-based collecting functional groups grafted to the surface of the core. Optionally, the mercapto-based harvesting functional group is derived from at least one of butyl xanthate, isobutyl xanthate, amyl xanthate, isoamyl xanthate, and ethionine. Optionally, the average hydration particle size of the nano-sized lignin core is 100 nm-300 nm, and the polydisperse coefficient PDI is less than or equal to 0.2. In a second aspect, an embodiment of the present application provides a method for preparing the nano lignin-based desulfurization collector in the first aspect, the method comprising performing graft copolymerization reaction on a nano lignin dispersion, a quaternary ammonium salt type surfactant and a sulfhydryl collector in the presence of an inert atmosphere and a free radical initiator; The mass ratio of the nano-sized lignin solid in the nano-sized lignin dispersion liquid to the sulfhydryl collector is 1 (5-10), the mass of the free radical initiator is 10% -30% of the mass of the sulfhydryl collector, the grafting copolymerization reaction temperature is 50-90 ℃, and the grafting copolymerization reaction time is 20-30 hours. Optionally, the quaternary ammonium salt type surfactant is at least one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide. Optionally, the free radical initiator is one of ammonium persulfate, potassium persulfate and azo diisobutylamidine hydrochloride. Optionally, the preparation method of the nano-scale lignin dispersion liquid comprises the following steps: Dissolving the pretreated lignin in an organic solvent, and stirring and dissolving to obtain a lignin organic solution; adding deionized water into the lignin organic solution, and performing dilution-induced self-assembly treatment to precipitate lignin to form nano particles, so as to obtain nano lignin suspension; transferring the nano lignin suspension into a pretreated dialysis bag, and performing dialysis and purification treatment to remove the organic solvent and small molecular impurities, thereby obtaining nano lignin dispersion; the pretreatment of the dialysis bag comprises the steps of putting a dialysis tube into deionized water containing sodium bicarbonate and EDTA disodium salt for boiling, putting the dialysis tube into the deionized water containing EDTA disodium salt for boiling again after washing, and soaking the dialysis tube into ethanol water solution for standby. Optionally, the organic solvent is at least one of methanol, absolute ethanol, isopropanol, acetone, tetrahydrofuran and N, N-dimethylformamide. Optionally, the pretreatment lignin is one of alkali lignin, lignosulfonate, enzymatic hydrolysis lignin and organic solvent lignin. Optionally, in the lignin organic solution, the mass concentration of lignin is 1 mg/mL-50 mg/mL. Optionally, in the dilution-induced self-assembly treatment, the volume ratio of the deionized water to the lignin organic solution is (3-50): 1. Optionally, in the dialysis purification treatment, deionized water is replaced every 8-12 hours, the molecular weight cut-off of a dialysis bag is not less than 3500 Da, and the dialysis time